Development of Synthetic Reactions Using New Types of Lewix Acid Catalysts

使用新型 Lewix 酸催化剂的合成反应的进展

基本信息

批准号：
08555230
负责人：
KOBAYASHI Shu
金额：
$ 7.55万
依托单位：
The University of Tokyo (1998)Tokyo University of Science (1996-1997)
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (A)
财政年份：
1996
资助国家：
日本
起止时间：
1996 至 1998
项目状态：
已结题

项目摘要

1.Catalytic Friedel-Crafts acylation of benzene and unactivated benzenes such as chlorobenzene and fluorobenzene has been successfully carried out using hafnium (IV) inflate and trifluoromethanesulfonic acid as catalysts. Both aromatic and aliphatic carboxylic acid chlorides reacted smoothly under the conditions to afford the corresponding aromatic ketones in good yields.2. Metal chlorides and some perchlorates and trifluoromethanesulfonates (triflates) of group 1-15 elements were screened in the Mukaiyama aldol reaction (an aldol reaction of an aldehyde with a silyl enol ether) for the purpose of finding Lewis acid catalysts stable in water. It was shown that metal compounds based on Fe(II), Cu(II), Zn(II), Cd(II), Pb(II) as well as the rare earths (Sc(III), Y(III), Ln(III)) were stable and active in water. Correlation between catalytic activity of these elements (cations) in water and hydration constants and exchange rate constants for substitution of inner-sphere water ligands (wate … More r exchange rate constant (WERC)) were found, and without exception metal compounds, which have both pKh values from 4.3 to 10.08 and WERC greater than 3.2x10^6 M^<-1> sec^<-1>, gave satisfactory yields in the aldol reaction.3. Development of polymer-supported catalysts is one of the most important tasks in organic synthesis. especially in the move towards clean and environmentally friendly chemical processes. We have developed an unprecedented polymer-supported Lewis acid, a microencapsulated scandium trifluoromethanesulfonate (scandium inflate) (MC Sc(OTf)_3). This new method for immobilizing a catalyst onto a polymer is based both on physical envelopment by the polymer and on electronic interaction between pi electrons of benzene rings of the polymer and a vacant orbital of the Lewis acid.A scanning electron microscopy (SEM) micrograph revealed that small capsules of MC Sc(OTf)_3 adhered to each other, and it was also shown by scandium energy dispersive X-ray (EDX) mapping that Sc(OTf)_3 was located all over the polymer surface. One of the most remarkable points is that the activating ability of MC Sc(OTf)_3 was shown to be superior to monomeric Sc(OTf)_3 by preliminary kinetic studies. The catalyst was readily prepared and maintained high activity. Moreover, it was recoverable and reusable, and was successfully applied to many useful carbon-carbon bond-forming reactions. Less

1。使用Hafnium（IV）膨胀（IV）膨胀和三氟甲磺酸作为催化剂，已成功地进行了苯和未激活的苯（例如氯苯和氟苯）的催化弗里德尔抗化。芳香族和脂肪族羧酸氯在条件下都平稳地反应，以获得相应的芳族酮的良好产量。2。在Mukaiyama Aldol反应中筛选了1-15组元素的金属氯化物，某些高氯酸盐和三氟甲磺酸盐（三氟甲磺酸盐）（三二醛反应）（醛的醛反应与Silyl enol ether），目的是找到水中稳定的水中的Lewis酸催化剂。结果表明，基于Fe（II），Cu（ii），Zn（ii），CD（II），Pb（ii）以及稀土（SC（III），Y（III），LN（III））的金属化合物稳定并且活跃在水中。发现了这些元素（阳离子）在水与水合常数的催化活性与替代内球形水配体（Wate…更多r汇率常数（WERC））的汇率常数，并且没有例外的金属化合物，它们具有PKH值，它们的PKH值在4.3到10.08到10.08至3.2x10^6 m^<-1> sect s suffers formes suff Suffers均可满足。 reaction.3. Development of polymer-supported catalysts is one of the most important tasks in organic synthesis. especially in the move towards clean and environmentally friendly chemical processes.我们已经开发了一种前所未有的聚合物支持的刘易斯酸，这是一种微囊化的三氟甲磺酸会（Scandium Emprate）（MC SC（OTF）_3）。这种将催化剂固定在聚合物上的新方法既基于聚合物的物理环境，又基于聚合物苯环的PI电子之间的电子相互作用，以及Lewis酸的空置轨道。A扫描电子显微镜（SEM）显微镜（SEM）显微照片显示了MC的小帽子（sc and and Mc sc（OTF），它与其他相关的镜头（OTFRES）相处得出了其他sc（OTF）。 X-ray (EDX) mapping that Sc(OTf)_3 was located all over the polymer surface.最引人注目的观点之一是，通过初步动力学研究，MC SC（OTF）_3的激活能力比单体SC（OTF）_3优于单体SC（OTF）。 The catalyst was readily prepared and maintained high activity. Moreover, it was recoverable and reusable, and was successfully applied to many useful carbon-carbon bond-forming reactions.较少的